CN103643281A - Preparation method of electrophoretic deposition carbon nanotube field emitter in aqueous solution - Google Patents
Preparation method of electrophoretic deposition carbon nanotube field emitter in aqueous solution Download PDFInfo
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- CN103643281A CN103643281A CN201310567298.XA CN201310567298A CN103643281A CN 103643281 A CN103643281 A CN 103643281A CN 201310567298 A CN201310567298 A CN 201310567298A CN 103643281 A CN103643281 A CN 103643281A
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Abstract
The invention discloses a preparation method of an electrophoretic deposition carbon nanotube field emitter in an aqueous solution, which comprises the following steps: treating a carbon nanotube through nitric acid ultrasonic treatment or using a heating condition to obtain a carboxylation carbon nanotube; 2)dispersing the carboxylation carbon nanotube obtained in the step 1) by using a proper amount of surfactant in deionized water in an auxiliary mode, performing microwave for 1-4 hours for fully dispersing the carbon nanotube; 3)centrifuging a carbon nanotube aqueous solution obtained in the step 2) for 10-30 minutes, discharging a supernate, finally acquiring the carbon nanotube water system electrophoresis liquid with conductivity of 5-10 mumS.cm<-1>; 4)disposing two blocks of metal pole plates in a parallel mode in the carbon nanotube water system electrophoresis liquid, wherein the spacing of the pole plates is controlled at 0.5-3cm, applying 30-60V direct current voltage between pole plates, depositing for 0.5-10 minutes and removing the metal pole plates and drying, and 5)annealing, which is an annealing step carried out at 380-550 DEG C.
Description
Technical field
The invention belongs to carbon nanotube cold cathode field of material preparation, be specifically related to a kind of in the aqueous solution electrophoretic deposition field emission body of Nano carbon tube to improve the method for its field emission stability.
Background technology
Carbon nanotube has the performance of a lot of excellences as field emmision material, the tip end surface that almost approaches theoretical limit is long-pending, high chemical stability, excellent conductivity, heat-conductive characteristic and physical strength, thereby carbon nanotube has extremely low field transmitting cut-in voltage, can tolerate great current density, and current delivery is very stable, therefore carbon nanotube is suitable as cold-cathode field emissive material very much, and the field emitting electronic source of preparing based on carbon nano-tube material is most promising cold cathode technology of preparing of future generation.
At present, the method for preparing field emission body of Nano carbon tube mainly contains two kinds of base types: growth method and transfer method.Carbon nanotube direct growth technique is comparatively complicated comparatively speaking, and growth temperature is high, and substrate material is had to considerable restraint, and large area deposition cost is high, also slightly inadequate with substrate bonding strength, thereby has a strong impact on launch stability and work-ing life.Transfer method mainly comprises silk screen printing and electrophoretic deposition.Wherein electrophoretic deposition can obtain very high sedimentation rate, is a kind of technique that has very much prospects for commercial application, and it is that a kind of cheapness, reproducibility are good, process and be widely used in the deposition technique of industrial circle under normal temperature.The speed size of electrophoretic deposition is irrelevant with the size of nano particle, thus the convenient settled layer that obtains even compact, and the current subject matter of electrophoretic deposition is that the sticking power between settled layer and substrate is poor.
And for industrial application, water system reaction has larger magnetism, and carbon nanotube has good dispersiveness and dispersion stabilization in water system, the detrimentally affect of the electrolysis aerogenesis that at present in water system, electrophoretic deposition mainly faces water to settled layer homogeneity and adhesive power.In water solution system, electrophoretic deposition carbon nanotube just must solve the electrolysis problem of water, and for the gas producing on pole plate, having at present can oxidized sacrifice layer (as active metal pole plate), ionogen, semi-permeable membranes or adopt pulse ac power supply to solve by introducing.Although electrophoretic deposition carbon nanotube does not exist electrolysis and the aerogenesis problem of water in organic solution, the dispersiveness of carbon nanotube and dispersion stabilization are not good, and adhesive power is very poor, and field emission body launch stability and the homogeneity of acquisition are undesirable.
Summary of the invention
The object of the invention is, the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution is proposed, the some shortcomings of preparing Carbon Nanotube Cold Cathode Field Emission Research body prior art for current electrophoretic deposition, utilize carbon nanotube in water solution system, compare in organic solvent better dispersion stabilization and and the greater advantages of water solution system in industrial application comparatively speaking, prepare the field emission body of Nano carbon tube with good launch stability and life-span.
The present invention is achieved by the following technical solutions, and in a kind of aqueous solution, the preparation method of electrophoretic deposition field emission body of Nano carbon tube, comprises the steps:
(1) ultrasonic by nitric acid (weight concentration is at 20-35%) or to process carbon nanotube under heating condition, obtain carboxylic carbon nano-tube again, and with supersound process 1-4h, with 0.45 μ m mixed cellulose ester water system filter membrane suction filtration, and use deionized water repetitive scrubbing, to washing lotion pH value be 6～7, obtain carboxylic carbon nano-tube;
The condition of described heating can be 120 ℃ of condensing refluxes;
(2) by the carboxylic carbon nano-tube that obtains in step (1) by proper amount of surfactant aid dispersion in (as 200ml, volume is nanotube more than 20 times) deionized water, ultrasonic 1-4h fully disperses carbon nanotube;
(3) by the carbon nano-tube aqueous solutions obtaining in step (2) centrifugal 10-30min under 3000-6000r/min, discard supernatant liquid, lower leafing go out thing more ultrasonic 10-30min be dispersed in deionized water, and then centrifugal 10-30min under 3000-6000r/min, discard supernatant liquid, lower leafing go out thing more ultrasonic 10-30min be dispersed in deionized water, repeat operation 2-10 time, remove the tensio-active agent being free in the aqueous solution, finally obtain specific conductivity and be controlled at 5～10 μ Scm
-1carbon nanotube water system electrophoresis liquid; Thereby effectively suppress the electrolysis of water;
(4) be placed in above-mentioned carbon nanotube water system electrophoresis liquid the pole plate of two blocks of metals (as 0.2 * 10 * 10mm) is parallel, polar plate spacing is controlled at 0.5～3cm, between two-plate, apply the volts DS of 30～60V, after deposition 0.5～10min, slowly take out metal polar plate, be placed horizontally at the interior 10h of stink cupboard above air-dry, as 24h natural air drying;
(5) anneal, anneal at 380～500 ℃ of temperature, or logical shielding gas nitrogen, carbonic acid gas or argon anneal;
Further, especially the metal polar plate after natural air drying in (4) is placed in the quartz boat of tube furnace, directly the temperature rise rate with 10 ± 2 ℃/min rises to a lower annealing temperature (450 ± 20 ℃), insulation 0.5～1h; Or first pass into shielding gas (N
2/ Ar), after 10min, with the temperature rise rate of 10 ℃/min, rise to 450 ℃ and be incubated 0.5～1h again.
Tensio-active agent described in step (2) is aniorfic surfactant sodium laurylsulfonate (SDS) or Sodium dodecylbenzene sulfonate (SDBS) or nonionic surface active agent triton x-100, add-on be 50mg(get nanotube quality 5-40% all can).The pole plate of metal is through clean etc. pretreated.
Metal polar plate material described in step (4) is stainless steel (316L), Cu, Al or Ti.
Preprocessing process described in step (4) is for first using washed with de-ionized water with acetone or alcoholic solvent ultrasonic cleaning again.
The present invention passes through nitric acid treatment, in carbon nano tube surface, introduce carboxyl, thereby greatly improve carbon nanotube at the adhesive power of metal substrate surface, again by repeatedly ultrasonic centrifugal, free tensio-active agent, carbon nano-tube aqueous solutions specific conductivity is controlled at proper range, thereby effectively suppress the electrolysis of water in electrophoresis process, impose again high DC electric field, improve on the one hand sedimentation velocity, further improve on the other hand carbon nanotube sticking power, the final field emission body of Nano carbon tube with excellent field emission performance that obtains.
By functionalization and the selection to metal polar plate material of carbon nanotube, the present invention has solved the problem that electrophoretic deposition is prepared field emission body of Nano carbon tube poor adhesion effectively; By repeatedly ultrasonic, centrifugal electrical conductivity of solution is controlled to suitable scope, has effectively solved electrolysis and the inhomogeneous problem of deposition of electrophoretic deposition carbon nanotube water in the aqueous solution, finally obtain having the field emission body of Nano carbon tube of stationary field emitting performance.
The invention has the beneficial effects as follows: a kind of method of improving electrophoretic deposition field emission body of Nano carbon tube launch stability in the aqueous solution providing mainly contains two aspect features: first, by functionalization and the selection to metal polar plate material of carbon nanotube, the present invention has solved the problem that electrophoretic deposition is prepared field emission body of Nano carbon tube poor adhesion effectively; Strengthen the bonding strength of carbon nanotube and metal base, increased electron emission stability and the work-ing life of field emission body.Second, by simple, repeatedly ultrasonicly centrifugal electrical conductivity of solution is controlled to suitable scope, effectively solved electrolysis and the inhomogeneous problem of deposition of electrophoretic deposition carbon nanotube water in the aqueous solution, effectively improve the dispersing uniformity of carbon nanotube in radiator, obtained the field emission body of Nano carbon tube with stationary field emitting performance.
Accompanying drawing explanation
Fig. 1 is electrophoretic deposition device schematic diagram.
Embodiment
1. the preparation of carboxylic carbon nano-tube:
Original carbon nanotube purchased from Chengdu organic chemistry company limited is placed in to the salpeter solution of suitable dilution, ultrasonic 3h or 120 ℃ of condensing reflux 3h, use again 0.45 μ m cellulose mixture film suction filtration, and with deionized water, to be washed till filtrate pH value be 6～7, obtain carboxylic carbon nano-tube.
2. the dispersion of carbon nanotube:
Above-mentioned gained carboxylic carbon nano-tube is placed in to 200ml or above deionized water, and under tensio-active agent aid dispersion, ultrasonic 3h obtains carbon nanotube aqueous dispersions.
3. the preparation of carbon nanotube water system electrophoresis liquid:
The centrifugal 20min of rotating speed by above-mentioned carbon nanotube aqueous dispersions with 4000r/min, discards supernatant liquid, lower leafing go out thing again ultrasonic 20min be scattered in 200ml deionized water, so repeatable operation for several times until ultrasonic rear gained electrical conductivity of solution at 10 μ Scm
-1below, then with the centrifugal 10min of 3000r/min, get supernatant liquid and obtain carbon nanotube water system electrophoresis liquid.
4. electrophoretic deposition:
As shown in Figure 1, two 0.2 * 10 * 10mm metal polar plates are used to acetone ultrasonic cleaning in advance, use again washed with de-ionized water, then be placed in parallel in above-mentioned carbon nanotube water system electrophoresis liquid, polar plate spacing 0.5～3cm, between two-plate, apply the volts DS of 30～60V, after deposition 0.5～10min, slowly take out metal polar plate, be placed horizontally at 24h natural air drying in stink cupboard.DC is direct supply, and 1 is electrophoresis chamber.
5. annealing:
Pole plate after above-mentioned natural air drying is placed in the quartz boat of tube furnace, directly the temperature rise rate with 10 ℃/min rises to 450 ℃, insulation 0.5～1h; Or first pass into shielding gas (N
2/ Ar), after 10min, with the temperature rise rate of 10 ℃/min, rise to 450 ℃ and be incubated 0.5～1h again.
Embodiment 1:
By 200mg carbon nanotube (purity approximately 95%, multi-walled carbon nano-tubes purchased from the growth of the Chengdu CVD of organic chemistry company limited method, caliber 20-30nm, length 10-30 μ m) join in 50ml nitric acid and 150ml deionized water mixing solutions, supersound process 3h, use again 0.45 μ m cellulose mixture film suction filtration, and with deionized water, to be washed till filtrate pH value be 6～7, obtain carboxylic carbon nano-tube.
Above-mentioned gained carboxylic carbon nano-tube is placed in to 200ml deionized water, adds 50mg sodium laurylsulfonate, ultrasonic dispersion 3h obtains carbon nanotube aqueous dispersions.
The centrifugal 20min of rotating speed by above-mentioned carbon nanotube aqueous dispersions with 4000r/min, discard supernatant liquid, lower floor leach thing again ultrasonic 20min be scattered in 200ml deionized water, so centrifugal ultrasonic 5 times, then with the centrifugal 10min of 3000r/min, get supernatant liquid and obtain carbon nanotube water system electrophoresis liquid.
150ml deionization is constant, and the nitric acid mixing solutions carboxylation reaction that adopts 40ml nitric acid or 60ml nitric acid to obtain obtains identical carboxylic carbon nano-tube.
Two 0.2 * 10 * 10mm stainless steel polar plates are used to acetone ultrasonic cleaning in advance, use again washed with de-ionized water, then be placed in parallel in above-mentioned carbon nanotube water system electrophoresis liquid, polar plate spacing 1cm, between two-plate, apply the volts DS of 60V, after deposition 5min, slowly take out, be placed horizontally at 24h natural air drying in stink cupboard.As adopting copper coin or the titanium plate of spacing 2cm, pole plate also can obtain identical result completely.
Stainless steel polar plate after above-mentioned natural air drying is placed in the quartz boat of tube furnace, passes into Ar, after 10min, with the temperature rise rate of 10 ℃/min, rise to 450 ℃ and be incubated 0.5h again.380 ℃, 420 ℃, 500 ℃ annealing are all without significantly difference.
Embodiment 2: sodium laurylsulfonate in embodiment 1 is replaced with to Sodium dodecylbenzene sulfonate or triton x-100, and other steps are with embodiment 1.
Embodiment 3: change supersound process 3h in carboxylic carbon nano-tube preparation process in embodiment 1 into 120 ℃ of condensing reflux 3h, other steps are with embodiment 1.
Embodiment 4: the stainless steel polar plate that uses in embodiment 1 electrophoretic deposition process is replaced with to aluminium sheet, copper coin or titanium plate.Other steps are with embodiment 1.
Embodiment 5: the electrophoretic deposition time in embodiment 1 is replaced with to 0.5min or 2min or 10min, and other steps are with embodiment 1.
Embodiment 6: change polar plate spacing in embodiment 1 electrophoretic deposition process into 0.5cm, voltage replaces with 30V, and other steps are with embodiment 1.
Embodiment 7: change polar plate spacing in embodiment 1 electrophoretic deposition process into 3cm, other steps are with embodiment 1.
Embodiment 8: annealing process in embodiment 1 is changed into and do not pass into shielding gas, be directly warmed up to 450 ℃, other steps are with embodiment 1.
The present embodiment has only provided the concrete application examples of part, but for a person skilled in the art, also can design the variation being equal to according to above enlightenment, and this is still considered to be covered by among the scope of protection of present invention.
Claims (6)
1. a preparation method for electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution, is characterized in that comprising the steps:
(1) ultrasonic or to process carbon nanotube under heating condition, obtain carboxylic carbon nano-tube again at 20-35% nitric acid by weight concentration, supersound process 1-4h, with 0.45 μ m mixed cellulose ester water system filter membrane suction filtration, and use deionized water repetitive scrubbing, to washing lotion pH value be 6～7, obtain carboxylic carbon nano-tube;
(2) use proper amount of surfactant aid dispersion in deionized water the carboxylic carbon nano-tube obtaining in step (1), ultrasonic 1-4h fully disperses carbon nanotube;
(3) by the carbon nano-tube aqueous solutions obtaining in step (2) centrifugal 10-30min under 3000-6000r/min, discard supernatant liquid, lower leafing go out thing more ultrasonic 10-30min be dispersed in deionized water, and then centrifugal 10-30min under 3000-6000r/min, discard supernatant liquid, lower leafing go out thing more ultrasonic 10-30min be dispersed in deionized water, repeat operation 2-10 time, remove the tensio-active agent being free in the aqueous solution, finally obtain specific conductivity and be controlled at 5～10 μ Scm
-1carbon nanotube water system electrophoresis liquid; Thereby effectively suppress the electrolysis of water;
(4) by two parallel being placed in above-mentioned carbon nanotube water system electrophoresis liquid of metal polar plate, polar plate spacing is controlled at 0.5～3cm, between two plates, apply the volts DS of 30～60V, after deposition 0.5～10min, slowly take out metal polar plate, be placed horizontally at natural air drying in stink cupboard;
(5) anneal, anneal at 380～500 ℃ of temperature, or logical shielding gas nitrogen, carbonic acid gas or argon anneal.
2. the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution according to claim 1, the condition that it is characterized in that described heating is 120 ℃ of condensing refluxes.
3. the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution according to claim 1, is characterized in that tensio-active agent described in step (2) is aniorfic surfactant sodium laurylsulfonate (SDS) or Sodium dodecylbenzene sulfonate (SDBS) or nonionic surface active agent triton x-100.
4. the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution according to claim 1, is characterized in that described in step (4), metal polar plate material is stainless steel, Cu, Al or Ti.
5. the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution according to claim 1, is characterized in that preprocessing process described in step (4) is for first using washed with de-ionized water with acetone or alcoholic solvent ultrasonic cleaning again.
6. the preparation method of electrophoretic deposition field emission body of Nano carbon tube in the aqueous solution according to claim 1, it is characterized in that the metal polar plate after natural air drying in (4) to be placed in the quartz boat of tube furnace, directly the temperature rise rate with 10 ± 2 ℃/min rises to a lower annealing temperature (450 ± 20 ℃), insulation 0.5～1h; Or first pass into shielding gas (N
2/ Ar), after 10min, with the temperature rise rate of 10 ℃/min, rise to 450 ℃ and be incubated 0.5～1h again.
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Cited By (2)
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| CN105002541A (en) * | 2015-08-07 | 2015-10-28 | 上海海事大学 | Automated electrolytic tank |
| CN105002541B (en) * | 2015-08-07 | 2017-05-24 | 上海海事大学 | Automated electrolytic tank |
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